Dyeing process



Patented Oct. 27, 1936 UNITED STATES PATENT OFFICE DYEING PROCESS ofDelaware Serial No. 14,27

No Drawing. Application :prll 2, 1935,

18 Claim.

This invention relates to new dyeing and printing processes and moreparticularly refers to improved processes for dyeing and printing cottonand related textile materials by means of mixtures of ice color couplingcomponents and di-- azoimino compounds to be more fully describedhereafter.

Certain classes of diazoimino compounds which are well adapted for usein the dyeing and printing of textile materials have been described inthe prior art. The stabilizing components of these compounds are allcharacterized in that they are hydrocarbons containing an amino or iminogroup and one or more carboxylic or sulfonic acid groups. With theexception of the aforementioned substituents, however, the stabilizingcomponents are composed entirely of carbon and hydrogen. For a moredetailed description of compounds of this type reference may be made toU. S. Patents 1,882,560, 1,882,561, 1,882,- 562 and 1,982,681.-

Since the coupling of diazotized 'af'ylamines and tetrazotized .arylenediamines with various components is profoundly affected by the structureof such components it is exceedingly important that-great care beexercised in selecting coupling components. This is true to an evengreater extent in the production of diazoimino compounds because ofadditional characteristics which these compounds must possess. Forexample, a satisfactory diazoimino compound must couple in such mannerthat the resulting product is stable in neutral or alkaline solution.Moreover, the product must be readily soluble. f equal importance is theability of these compounds to hydrolyze readily and completely in orderthat the diazo base might be satisfactorily regenerated. It is obviousfrom a consideration of these factors that the structure of thestabilizing component is of utmost importance and that the presencethereon of certain substituents,

as well as the position of these substituents, produces a far reachingefiect upon the characteristics of the resulting compound.

It is an object of this invention to devise an entirely new process fordyeing and printing textile materials. A further object is to produce acolor imparting medium which may exist in the form of dry powders,aqueous pastes, aqueous solutions, or other types of solutions. A stillfur ther object is to produce a dyeing and printing medium whichcontains a class of diazoimino compounds which is entirely unrelated toany heretofore used; A still further object is to utilize a unique andheretofore unknown class of diazoimino compounds in the production ofice colors on, cotton fibers. Additional objects will become apparentfrom a consideration of the following description and claims.

These objects are attained according to the herein described inventionwherein dyeing and printing compositions are made which contain thecustomary coupling components, assistants and the like, in addition todiazoimino compounds produced by coupling a diazotlzed aromatic 10 amineor tetrazotized aromatic diamine with a heterocyclic' compound having animino-containing radical substituted thereon. In a more restricted sensethis invention 'is concerned with dyeing and printing compositionscontaining an ice color coupling component and a water and alkalisoluble diazoimino compound produced by coupling a diazotized aromaticamine, capable of use in the production of ice colors, with aheterocycllc compound having an imino-containing radical substitutedthereon through the imino group of which coupling takes place, andfurthermore containing one or more water-solubilizing groups; Thisinvention pertains, in its preferred embodiment, to dyeing and printingcomposi tions containing approximately molecular equivalent quantitiesof an ice color coupling component, preferably arylamides of2-3-hydroxynaphthoic acid or acyl-acet-arylides, and diazoiminocompounds produced by coupling diazotized aromatic amines, capable ofuse in the production of ice colors, with" furfuryl-aminoacetic acid ortetra-hydro-furfuryl-amino-acetic acid.

The invention may be more readily understood by a consideration of thefollowing illustrative examples in which the quantities are stated inparts by weight:

Example 1 330 parts of the dry diazoimino compound of the followingformula:

| cmcooNa N=N v 0 I \CH:O/. on

i H H o1 obtained by the action of diazotized4-chloro-2- amino-tolueneon furfuryl-ammo-acetic acid, were ground with 280 parts of theortho-toluidide of 2-3-hydroxy-naphthoic acid producing a yellow powder.

A printing paste of the following composition was prepared:

Parts The above mixture 4.0 Cellosolve 4.0 Sodium hydroxide solution(35%) 2.0 Sulfonated castor oil 1.0 Water (warmed to 140 F.) 29.0 Starchtragacanth thickener 60.0

and printed from an engraved roll onto cotton piece goods. The printedmaterial was dried thoroughly and then aged for 2 minutes in the vaporsarising from a boiling solution of 4 parts of acetic acid (56%) and 1part of formic acid (85%) in 15 parts of water. The prints were rinsed,soaped, again rinsed, and then dried. Bright red dyeings of goodfastness properties were obtained, due to the formation of the dye ofthe formula:

Example 2 N t l l.

produced by the action of diazotized 4-ch1oro-2- amino-anisole onfurfuryl-amino-acetic acid was mixed with 300 parts of theortho-anisidide of 2-3-hydroxy-naphthoic acid. Cotton piece goods wereprinted with a paste prepared from this composition by the proceduresimilar to that described in Example 1. After color development andsoaping of the prints, the pattern was developed as a brilliant bluishred due to the formation of the color of the probable formula:

oom

on 1 0 ONE? om Emdmple 4 350 parts of the water soluble diazoiminocompound of the following formula:

N=NN 0 Hz- H:

1 obtained by the action of diazotized 4-chloro-2- amino-anisole ontetra-hydro-furfuryl-aminoacetic acid, and 225 parts ofaceto-acetyl-pphenetidine were stirred with 600 parts of ethyl alcohol,300 parts of sodium hydroxide solution of 30% strength were added,followed by 1400 parts of water. The mass was stirred until completesolution was obtained, then filtered.

A printing paste of the following composition was prepared:

Parts The above solufinn 20 Water 20 Starch tragacanth thickener 0Cotton goods were printed and aged by the procedure given in Example 1.Bright yellow dyeings of very good fastness to light were obtained, dueto the formation of the dye of the formula:

OCH:

COCH:

omoo CHO ONHOQNHCOCHOOCH; 43H: z

Example 3 350 parts of the water soluble diazoimino compound of thefollowing structural formula:

OCH:

CHaCOONa Example 335 parts of the dry diazoimino compound of thefollowing formula:

OCH: CHz-COONa N=NN o CH -CH (3H2 H; CH:

7 .phen'yl,- naphthalene, anthracene, azobenzene, di

obtained by the action of diazotized 4-chloro-2- amino-anisole ontetra-hydro-furfuryl-aminoacetic acid, were ground with 240 parts ofacetoacetyl-p-phenetidine producing a gray powder. 12 parts of thismixture were dissolved in 40 parts of sodium hydroxide solution (35%)and 950 parts of water. Cotton piece goods were padded in this solution,then passed through squeeze rollers and dried. The padded goods wereaged under the same conditions given in Example 1, rinsed,

soaped, rinsed and dried. Bright yellow dyeings of good fastness tolight were obtained. The color was identical with that producedaccording to Example 4.

The following table lists a number of other representative dyeing andprinting compositions, suitable for the coloring of textile fabrics asillustrated in the above examples:

phenyl ether, diphenylamine and carbazole series are quite satisfactory.The aforementioned and related amines may have substituted thereon oneor more radicals such'as, for purposes. of illustration, alkyl, alkoxy,halogen, nitro, acylamino, benzoylamino, sulfonamido trifluoro-methyl,and the like groups. It is usually advisable that these amines should befree from groups which confer No. Base Stabilizer Coupling component g gg l 4-chloro-2-aminotoluene Tetra-hydrolurfuryl-omino-aceticacid.2-hydroxy-3-naphthoy1-o-toluidine Red. 2 do do2-hydroxy-3-nuphthoyl-o-phenetidine Scarlet. 3 do do Sodium compound of2-hydroxy-3- Red.

naphthoyl-m-xylidine. 4 4-chloro-2-amino- .do2-hydroxy-3-naphthoyl-o-anisidine. Do. 5 4-nitro-2-amino-nnisnle do 2-hdroxy-3-naphthoyl-3'-nitro-ani]i11e- Bluish-red. 6 Diamsidine .do So iumcompound of 2-hydroxy-3- Blue.

- nafhthoyl-aniline. 7 4-iuroyl-arnino-2,5-diethoxy-aniline do o.-. Do.8 4-carilliomethoxy-amino-2,5-dimethoxydo 2-hydroxy-3-naphthoyl-aniliDo.

an 1118. 9 3-chloro-aniline .do 2-hydroxy-3-naphthoyl-o'anisidinen" Red.10 5-nitro-2-amin0-anisoIe do Sodium compound of 2-hydroxy-3- Bordeaux.

- naphthoyl-wnaphthylamirw. l1 2,5-dichloro aniline'l-(iugiuryl-amino)-ethane-2-sulfonic Diaceto-acetyl-o-tolidine Yellow.

' aci 12 4-iuroyl-amino2,5-dimethoxy-aniline---. Sodium compound of2-hydroxy-3- Red-blue.

. naphthoyl-o-toluidine. 13 4-ethoxy-4-amino-2-5'-dimethoxy-azo- Sodiumcompound of 2-hydroxy-3- Black.

7 benzene. naphthoyl-a-nephthylamine. 14 4-chloro-2-amino-anisoleAceto-acetyLp-phenetidine Yellow. 154-benzoyl-amino-2,5-diethoxy-aniline.- 2-hydroxy-anthracene-3-carboxyl1cGreen.

acid-o-toluidide. 16 4-chloro-2-amino-toluene Sodium compound of2-hydroxy-3- Red.

. naphthoyl-o-toluidine. 17 do Diaceto-acetyl-o-tolidine-sulione l8Aniline do 19 4'-ethoxy-i-aminodiphenyl-amine2-hydroxy-3-naphtboyl-amline 20 Dianisidine .do d0 o. 21 doFmfuryl-amino-acetic acid 2-hydroxy-3-naphtboyl-o-tpluidme Do. 223-benzoyl-amino-4-methoxy-aniline ..do Z-hydroxy-El-naphthoyl-amhne.Bordeaux. 23 4- l:arbomethoxy-amino-2,fi-diethoxyani- .-.do2-hydroxy-3-naphthoyl-o-tolu1dme Blue.

1116. 24 4-benzoyl-amino-2-methoxy-5-methyldo' Sodium compound of2-hydroxy-3- Violet aniline. naphthoyl-aniline. 254-ch1oro-2-amin0-toluene Amixturc oi lurluryl-amino-acetic Sodiumcompound of 2-hydroxy-3- Red.

acid and:gtra-hydro-furiuryl-aminonaphthoylb-toluidine. ace 1c ac 26 doB-hydroxy othyl-iurluryl-amine- Sodium compound oi 2-hydroxy-3- Scarlet.

. naphthoyl-o-phenetidme. 27 do a-pyrldyl-amino-ecetic acid Sodiumcompound of 2-hydroxy-3- D0.

na hthoyl-o-phenetidine. 23 4- h10 2-amino-anisoleAmixtureofturiuryl-amino-aceticacid p-ch or-anilideoi2-hydroxy-carbezole- Brown.

and ticltra-hydro-iuriuryl-amino-ace- 3-carboxylic acid.

cac 29 4-benzoyl-amino-2.5-diethoxy-anilinc..;. .do o-toluidideoi2-hydroxy-anthracene-3- Green.

, carboxylic acid.

It is to be understood that the aforementioned examples are illustrativemerely of a relative few of the many modifications of the present invention. It is contemplated that the individual components, the proportionsthereof, the conditions of reaction and related features thereof may bevaried widely without departing from the scope of this invention.

In place of the diazoimino compounds referred to supra it is to beunderstood that other diazoimino compounds which contain as astabilizing component a' heterocyclic radical having substitutedthereon: an imino-containing radical and one or more water-solubilizinggroups may be used. Primary arylamines and arylene diamines which aresuitable for use in the production of ice colors may be used inmanufacturing these diazoiinino compounds. In this connection it may bestated that amines of" the benzene, di-

ride, 3-amino-carbazole, alpha-amino-anthraquinone,2,5-diethoxy-aniline, 5-methyl-2-methoily-aniline,5-chloro-2-amino-anisoie and 4-chloro-4'-amino-2,5'-diethoxy-azobenzene.

As in the case of the arylamines, the stabilizing components may also bevaried within a considerable range in accordance with the presentinvention. These stabilizing components are quite unrelated to anyheretofore known or used in that they arenot hydrocarbon derivatives butare heterocyclic compounds containing one or more hetero atoms andhaving an imino-containing radical substituted thereon. I Coupling takesplace through the imino group of the aforementioned radical. It iscontemplated that additional groups may be substituted upon theheterocyclic nucleus on the component in such manner, that theyinterfere or prevent this coupling from taking place in the describedmanner. In order that the resulting diazoimino compounds may be solublein water and/or alkali it is advisable to substitute one or morewater-solubilizing groups upon the stabilizing component selected. Thesewater-solubilizing groups are, for instance, carboxyl, sulfonic acid,hydroxyl, sulfinic acid, sulfato, and the like. The number and characterof watersolubilizing groups which are desirable will depend to a greatextent upon the diazo base selected and the purposes for which theresulting compounds are to be used. In general, the carboxylic acid andsulfonic acid groups are preferred. It is ,to be understood, however,that one or more of the additional solubilizing groups referred to orgroups suggested thereby may be used in place of or in addition to thecarboxylic and/ or sulfonic acid group. A few representative stabilizingcompounds selected in accordance with the above instructions are:Furfuryl-sorbitylamine, tetra-hydro-furfuryl-sorbityl-amine, 4-methylamino-Z-furoic acid, 3-methylaminobenzopyrane-ar.-sulfonic acid,dioxanylaminoacetic acid, 3-(l'-methyl-morpholino)-glycine,fl-thienyl-taurine, a-thienyl-glucamine, (1:4-dimethyl-piperazino)-methyl-glycine, p-sulfo-phenyl-furfuryl-amine,p-hydroxy-cyclohexyl-tetrahydro-furfuryl-amine, di-furfuryl-amino-4,4'-dicarboxylic acid and p-sulfato-ethyl-tetra-hydro-furfuryl-amine.

Many of the diazoimino compounds produced in accordance with the presentinvention may be represented by the following general formula:

wherein aryl represents an aryl nucleus adapted for use as a componentof an ice color, R1 represents an alkyl, carbo-cyclyl,carbo-cyclyl-alkyl, hetero-cyclyl, or hetero-cyclyl-allwl radical, R2represents a hetero-cyclyl or hetero-cyclyl-alkyl radical, and R1 and/orR2 contains one or more water-solubilizing groups.

Diazoimino compounds referred to herein which are .of optimum value overa wide range of. conditions and uses may be represented, for the mostpart, by the following general formula:

wherein R represents the residue of a diazotized amine of the benzene ornaphthalene series, free from water-solubilizing groups, and Zrepresents a furane derivative having an imino-containing radicalsubstituted thereon, said furane derivative containing atleast onewater-solubilizing group.

Coupling components which are particularly adapted for use herein arethose referred to by one familiar with the art as ice color couplingcomponents. Among these components mention may be made of the following:

(1) Arylamides of hydroxy-aryl-carboxylic acids, such as the arylides of2-3-hydroxy-naphthoic acids, 2-hydroxy-carbazole-3-carboxylic acid,7-hydroxy-alpha-naphtho-carbazole-6-carboxylic .acid,hydroxy-indole-carboxylic acids, hydroxy diphenylamine-carboxylic acids,hydroxyphenanthrene-carboxylic acids, etc. The arylamides may beproduced from the usual primary arylamines free from water solubilizinggroups, such as aniline, the halogenated anilines, toluidines,substituted toluidines, amino-phenol-ethers and substitution products,naphthylamines and their substitution products, etc.

(2) Acyl-acetyl derivatives of arylamines, such as aceto-acetyl,benzoyl-acetyl, and terephthaloyl-bis-acetyl derivatives of primaryarylamines and diamines free from water-solubilizing groups.

(3) Naphthols such as alphaand beta-naphthol.

(4) Acyl-naphthols such as 4-benzoyl-1-naphthol and 4-acetyl-1-naphthol.

(5) Aryl-alkyl-pyrazolones.

(6) Dihydroxy-quinolines.

In general, it may be stated that the arylides of. 2-3-hydroxy-naphthoicacid and acyl-acetyl derivatives of arylamines are preferred for useherein. It is to be understood that the invention is not restrictedthereto, however, since the other ice color coupling components referredto supra, and the numerous additional components suggested thereby, arealso capable of use herein.

purposes it issometimes helpful to select a mixture of. diazoiminocompounds and/or coupling components, and the present invention isunderstood to-be susceptible to such modification. The proportion ofdiazoimino compound and coupling component present in the mixture may bevaried within considerable range, although it is advisable that they bepresent in approximately molecular equivalent quantities. The customarydyeing and printing assistants may be incorporated in the.

mixture when desired. When the coupling components are arylamides ofhydroxy-naphthoic acids or related compounds they may be used in theform of thefree acids or as salts, preferably in the form of alkalimetal salts. It is clear from a consideration of the precedinginstructions that the resulting mixtures may be in the form of drypowders, aqueous pastes, aqueous solutions or other types of solutions,and "when dyeing and printing compositions are mentioned in the presentspecification andclaims it is understood that r they embrace theaforementioned types of mixtures. When solutions or aqueous pastes ofthe diazoimino compounds are produced it is advisable to make themsufficiently alkaline to prevent hydrolysis of the diazoimino compoundsto'the parent diazo salts. It is frequently advantageous to utilizeorganic solvents in the preparation of these dyeing and printingsolutions. Organic solvents of particular value in this connection arewater-miscible solvents, such as methanol, ethyl alcohol, ethyleneglycol, alkyl ethers of. ethylene glycol, diethylene glycol, and thelike.

In imparting colors to textile fibers it is contemplated that thevarious procedures known to the art may be followed. For example, whentextile fibers are printed with pastes containing the describedcompositions color development may be eifected by subjecting the printsto the action of steam and a mild volatile acid, such as acetic and/orformic. acids. Moreover, the prints may be developed by immersion in aboiling saturated salt solution which contains a weak acid; such asacetic, phthalic, oxalic, citric, and the like acids. It is alsocontemplated that materials may be inmarks, such elevated temperaturesmay advantageously be achieved either by the use of heated solutions orby the use of steam, and wherein the heated solutions and steam maycontain the desired hydrolyzing agents.

For a more detailed discussion of diazoimino compounds suitable for useherein reference may be had to copending application Serial No. 14,271,filed April 2, 1935, wherein these compounds are described and claimed.

By means of the present invention an entirely new class of diazoiminocompounds is utilized in the production of superior dyes and prints.These compounds are quite dissimilar to any heretofore used since theyare not hydrocarbon derivatives but are derivatives of heterocyclfccompounds. Due to the presence of one or more hetero atoms and due tothe configuration of these diazoimino compounds it is possible toproduce superior colors readily and economically. The stability of thesediazoimino compounds is quite marked, while at the same time the easewith which they revert to the parent diazo salt upon treatment withsuitable hydrolyzing agents is most pronounced. The compounds describedherein are quite compatible with assistants, penetrating agents,thickeners, alkalies, solvents and the numerous other accessories usedin the production of ice color dyes and prints. The resulting colors areexceedingly uniform and level and are exceptionally fast to laundering.

As many apparently widely diiferent embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that the invention is not limited to the specific embodimentsthereof except as defined in the appended claims.

We claim:

1.Dyeing and printing compositions which comprise an ice color couplingcomponent and a diazoimino compound having the following generalformula:

wherein R represents the residue of a diazotized aromatic amine ortetrazotizedaromatic diamine, Z represents the radical ofa heterocycliccompolmd having an imino-containing radical substituted thereon couplingtaking place through the imino group of the aforementioned substituent,said heterocyclic derivative containing at least one water-solubilizinggroup, and n represents the integer 1 or 2.

2. Dyeing and printing compositions which comprise anice color couplingcomponent and a diazoimino compound having the following generalformula:

wherein R represents the residue of a diazotized aromatic amine ortetrazotized aromatic diamine of the benzene or naphthalene series, freefrom water-solubilizing-groups, Z represents the radical of aheterocyclic compound havingan iminocontaining radical substitutedthereon coupling taking place through the imino group oftheaforementioned substituent, said heterocyclic derivative containing atleast one water-solubilizing group, and n represents the integer 1 or 2.

3. Dyeing and. printing compositions which comprise an ice colorcoupling component and a diazoimino compound having the followinggeneral formula:

wherein Rrepresents the residue of a diazotized aromatic amine ortetrazotized aromatic diamine, Z represents the radical of a furanederivative having an imino-containing radical substituted thereoncoupling taking place through the imino group of the aforementionedsubstituent, said iurane derivative containing at least onewatersolubilizing group, and n represents the integer I or 2;

'4. Dyeing and printing compositions which comprise an ice colorcoupling component and a diazoimino compound having the followinggeneral formula:

wherein R represents the residue of a diazotized aromatic amine ortetrazotized aromatic diamine of the benzene or naphthalene series, freefrom water-solubilizing groups, Z represents the radical of a furanederivative having an imino-containing radical substituted thereoncoupling taking placethrough the imino group'of the aforementionedsubstituent, said furane derivative containing at least onewater-solubilizing group, and n represents the integer lor 2.

\ 5. Dyeing and. printing compositions which comprise. an" ice colorcoupling component and a. diazoimino compound having the followinggeneral formula:

wherein R represents the residue of a diazotized amineof the benzene ornaphthalene series, free from-water-solubilizing groups, and Zrepresents a furane derivative having an imino-containing radicalsubstituted thereon coupling taking place through the imino group of theaforementioned substituent, saidfurane derivative containing at leastoneWater-solubilizing group.

6. Dyeing and printing compositions which comprise an arylamide of2-3-hydroxy-naphthoic acid and a diazoimino compound having thefollowing general formula:

wherein R represents the residue of an aromatic amine of the benzeneseries, free from carboxylic or sulfonic acid groups. I I

8. Dyeing and printing compositions which comprise an arylamide of2-3-hydroxy-naphthoic CHaC OONa wherein R represents the residue of anaromatic amine of the benzene series, free from carboxylic or sulfonicacid groups.

' 9. Dyeing and printing compositions which comprise anacyl-acet-arylide and a diazoimino compound having the following generalformula:

wherein R represents the residue of a diazotized amine of the benzene ornaphthalene series, free from water-solubilizing groups, and Zrepresents a furane derivative having an imino-containing radicalsubstituted thereon coupling taking place through the imino group of theaforementioned substituent, said furane derivative containing at leastone water-solubilizing group.

10. A process for imparting color to textile fihers which comprisestreating said fibers with a composition comprising an ice color couplingcomponent and a diazoimino compound having the following generalformula:

wherein R represents the residue of a diazotized aromatic amine ortetrazotized aromatic diamine, Z represents the radical of aheterocyclic compound having an imino-containing radical substitutedthereon coupling taking place through the imino group of theaforementioned substituent, said heterocyclic derivative containing atleast one water-solubilizing group, and n represents the integer 1 or 2,and developing the treated fibers by subjecting them to the action of ahvdrolyzing agent.

11. A process for imparting color to textile fibers which comprisestreating said fibers with a composition comprising an ice color couplingcomponent and a diazoimino compound having the following generalformula:

wherein R represents theresidue of a diazotized aromatic amine ortetrazotized aromatic diamine of the benzene or naphthalene series, freefrom water-solubilizing groups, Z represents the radicalof aheterocyclic compound having an imino-containing radical substitutedthereon coupling taking place through the imino group of theaforementioned substituent, said heterocyclic deriva-.

wherein R represents the residue of a diazotized aromatic amine ortetrazotized aromatic diamine, Z represents the radical of a furanederivative having an imino-containing radical substituted thereoncoupling taking place through the imino group of the aforementionedsubstituent, said furane derivative containing at least onewatersolubllizing group, and n represents the integer 1 or 2, anddeveloping the treated fibers by sub- .iecting them to the action of aweak acid at elevated temperatures.

13. A process for imparting color to textile fibers which comprisestreating said fibers with a composition comprising an ice color couplingcomponent and a diazoimino compound having the following generalformula:

wherein R represents the residue of a diazotized aromatic amine ortetrazotized aromatic diamine of the benzene or naphthalene series, freefrom water-solubilizing groups, Z represents the radical of a furanederivative having an imino-containing radical substituted thereoncoupling taking place through the imino group of the aforementionedsubstituent, said furane derivative containing at least onewater-solubilizing group, and n represents the integer 1 or 2, anddeveloping the treated fibers by subjecting them to the action of a weakacid at elevated temperatures.

14. A process for imparting color to textile fibers which comprisestreating said fibers with a composition comprising an ice color couplingcomponent and a diazoimino compound having the following generalformula:

wherein R represents the residue of a diazotized amine of the benzene ornaphthalene series, free from water-solubilizing groups, and Zrepresents a furane derivative having an imino-containing radicalsubstituted thereon coupling taking place through the imino group of theaforementioned substituent, said furane derivative containing at leastone water-solubilizing group, and developing the treated fibers bysubjecting them to the action of acetic or formic acid at elevatedtemperatures.

15. A process for imparting color to-cotton fibers which comprisestreating said fibers with a composition comprising an arylamide of 2-3-hydroxy-naphthoic acid and a diazoimino compound having the followinggeneral formula:

wherein R represents the residue of a diazotized amine of the benzene ornaphthalene series, free from water-solubilizing groups, and Zrepresents a furane derivative having an imino-containing radicalsubstituted thereon coupling taking place through the imino group of theaforementioned substituent, said furane derivative containing at leastone water-solubilizing group, and developing the treated fibers bysubjecting them to the action of acetic or formic acid at elevatedtemperatures.

16. A process for imparting color to cotton fibers which comprisestreating said fibers with a composition comprising an arylamide of 2-3-hydroxy-naphthoic acid and a-diazoimino compound having the followinggeneral formula:

CHaCOONa R-N=N- o cmo cn wherein It represents the residue of anaromatic amine of the benzene series, free from carboxylic or sulfonicacid groups, and developing the treated fibers by subjecting them to theaction of acetic and formic acid at elevated temperatures. g

17. A process for imparting color to cotton fibers which comprisestreating said fibers with a composition comprising an arylamide of 2-3-hydroxy-naphthoic acid and a diazoimino compound having the followinggeneral formula:

CHaOOONa RN=NN 'o omen cm H:CH:

wherein R represents the residue of an aromatic amine of the benzeneseries, free from carboxylic or sulfonic acid groups, and developing thetreated fibers by subjecting them to the action of acetic and formicacid at elevated temperatures.

18. A process for imparting color to cotton fibers which comprisestreating said-fibers with a composition comprising an acyl-acet-arylideand a diazoimino compound having the following general formula:

wherein R represents the residue of a diazotized amine of the benzene ornaphthalene series, free from water-solubilizing groups, and Zrepresents a furane derivative having an imino-containing radicalsubstituted thereon coupling taking place through the imino group of theaforementioned substituent, said furane derivative containing at leastone water-solubilizing roup, and developing the treated fibers bysubjecting them to the action of acetic and formic acid at elevatedtemperatures.

MILES A. DAHLEN. STANLEY R. DETRICK. ROBERT E. ETZELMILLER. FRITHJOFZWILGMEYER;

